US7524979B2ExpiredUtilityPatentIndex 52
Methods of making colorant compounds
Est. expirySep 27, 2022(expired)· nominal 20-yr term from priority
C09B 1/5145
52
PatentIndex Score
0
Cited by
48
References
66
Claims
Abstract
A process for preparing a colorant of the formula which comprises preparing a first reaction mixture by admixing leucoquinizarin and, optionally, quinizarin, an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, boric acid, and an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula followed by converting the colorant thus prepared to either an ester-substituted colorant by reaction with an esterification compound which is either an anhydride of the formula or an acid of the formula R 2 COOH in the presence of an optional esterification catalyst, or a urethane-substituted colorant by reaction with an isocyanate compound of the formula R 4 —N═C═C═O, and brominating the colorant thus prepared, wherein either conversion to ester or urethane can be performed before bromination or bromination can be performed before conversion to ester or urethane.
Claims
exact text as granted — not AI-modified1. A process for preparing a colorant of the formula
wherein Y is a hydrogen atom or a bromine atom, n is an integer of 0, 1, 2, 3, or 4, R 1 is an alkylene group or an arylalkylene group, R 2 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and R 4 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, which comprises (a) preparing a first reaction mixture by admixing (1) leucoquinizarin and, optionally, quinizarin, (2) an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, (3) boric acid, and (4) an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula
followed by (b) converting the colorant thus prepared to either (i) an ester-substituted colorant by reaction with an esterification compound which is either (A) an anhydride of the formula
or (B) an acid of the formula R 2 COOH in the presence of an optional esterification catalyst, or (ii) a urethane-substituted colorant by reaction with an isocyanate compound of the formula
R 4 —N═C═O,
and (c) brominating the colorant thus prepared, wherein either conversion to ester or urethane can be performed before bromination or bromination can be performed before conversion to ester or urethane.
2. A process according to claim 1 wherein conversion to ester or urethane is performed before bromination.
3. A process according to claim 1 wherein bromination is performed before conversion to ester or urethane.
4. A process according to claim 1 wherein conversion to ester is carried out and the resulting compound is of the formula
5. A process according to claim 1 wherein conversion to urethane is carried out and the resulting compound is of the formula
6. A process which comprises (a) preparing a first reaction mixture by admixing (1) leucoquinizarin and, optionally, quinizarin, (2) an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, wherein R 1 is an alkylene group or an arylalkylene group, (3) boric acid, and (4) an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula
(b) preparing a second reaction mixture by admixing (1) the alcohol-substituted colorant, (2) a carboxylic acid of the formula R 2 COOH, wherein R 2 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, (3) an optional esterification catalyst, and (4) a solvent and heating the second reaction mixture to form an ester-substituted colorant of the formula
and (c) forming a third reaction mixture by admixing (1) the ester-substituted colorant, (2) bromine, and (3) a solvent followed by quenching the third reaction mixture with water to form a brominated ester-substituted colorant and a salt thereof, of the formulae
wherein Y is a hydrogen atom or a bromine atom and n is an integer of 1, 2, 3, or 4.
7. A process which comprises (a) preparing a first reaction mixture by admixing (1) leucoquinizarin and, optionally, quinizarin, (2) an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, wherein R 1 is an alkylene group or an arylalkylene group, (3) boric acid, and (4) an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula
(b) preparing a second reaction mixture by admixing (1) the alcohol-substituted colorant, (2) bromine, and (3) a solvent followed by quenching the second reaction mixture with water to form a brominated alcohol-substituted colorant and a salt thereof, of the formulae
wherein Y is a hydrogen atom or a bromine atom and n is an integer of 0, 1, 2, 3, or 4; and (c) forming a third reaction mixture by admixing (1) the brominated alcohol-substituted colorant, (2) a carboxylic acid of the formula R 2 COOH, wherein R 2 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, (3) an optional esterification catalyst, and (4) a solvent and heating the third reaction mixture to form a brominated ester-substituted colorant of the formula
8. A process which comprises (a) preparing a first reaction mixture by admixing (1) leucoquinizarin and, optionally, quinizarin, (2) an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, wherein R 1 is an alkylene group or an arylalkylene group, (3) boric acid, and (4) an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula
(b) preparing a second reaction mixture by admixing (1) the alcohol-substituted colorant, (2) an isocyanate of the formula
R 4 —N═C═O
wherein R 4 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and (3) an optional catalyst and heating the second reaction mixture to form a urethane-substituted colorant of the formula
and (c) forming a third reaction mixture by admixing (1) the urethane-substituted colorant, (2) bromine, and (3) a solvent followed by quenching the third reaction mixture with water to form a brominated urethane-substituted colorant and a salt thereof, of the formulae
wherein Y is a hydrogen atom or a bromine atom and n is an integer of 1, 2, 3, or 4.
9. A process which comprises (a) preparing a first reaction mixture by admixing (1) leucoquinizarin and, optionally, quinizarin, (2) an aminobenzene substituted with an alcohol group of the formula —R 1 —OH, wherein R 1 is an alkylene group or an arylalkylene group, (3) boric acid, and (4) an optional solvent, and heating the first reaction mixture to prepare an alcohol-substituted colorant of the formula
(b) preparing a second reaction mixture by admixing (1) the alcohol-substituted colorant, (2) bromine, and (3) a solvent followed by quenching the second reaction mixture with water to form a brominated alcohol-substituted colorant and a salt thereof, of the formulae
wherein Y is a hydrogen atom or a bromine atom and n is an integer of 0, 1, 2, 3, or 4; and (c) forming a third reaction mixture by admixing (1) the brominated alcohol-substituted colorant, (2) an isocyanate of the formula
R 4 —N═C═O
wherein R 4 is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and (3) an optional catalyst and heating the second reaction mixture to form a brominated urethane-substituted colorant and a salt thereof, of the formulae
10. A process according to claim 1 wherein quinizarin is present in the first reaction mixture.
11. A process according to claim 10 wherein the quinizarin and the leucoquinizarin are present in relative amounts of at least about 5 moles of leucoquinizarin per every 95 moles of quinizarin.
12. A process according to claim 10 wherein the quinizarin and the leucoquinizarin are present in relative amounts of at least about 2 moles of leucoquinizarin per every 3 moles of quinizarin.
13. A process according to claim 10 wherein the quinizarin and the leucoquinizarin are present in relative amounts of at least about 1 mole of leucoquinizarin per every 1 mole of quinizarin.
14. A process according to claim 1 wherein no quinizarin is present in the first reaction mixture.
15. A process according to claim 1 wherein the alcohol-substituted aminobenzene is present in an amount of at least about 0.95 mole of alcohol-substituted aminobenzene per every one mole of (quinizarin plus leucoquinizarin).
16. A process according to claim 1 wherein the alcohol-substituted aminobenzene is present in an amount of no more than about 1.05 moles of alcohol-substituted aminobenzene per every one mole of (quinizarin plus leucoquinizarin).
17. A process according to claim 1 wherein the boric acid is present in an amount of about 1 mole of boric acid per every one mole of (quinizarin plus leucoquinizarin).
18. A process according to claim 1 wherein in the first reaction mixture a solvent is used which is methanol, ethanol, isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, or a mixture thereof.
19. A process according to claim 1 wherein the first reaction mixture is heated to a temperature of at least about 60° C.
20. A process according to claim 1 wherein the first reaction mixture is heated to a temperature of no more than about 120° C.
21. A process according to claim 1 wherein the first reaction mixture is heated for a period of time of at least about 3 hours.
22. A process according to claim 1 wherein the first reaction mixture is heated for a period of time of no more than about 24 hours.
23. A process according to claim 1 wherein the esterification compound is an anhydride and the alcohol-substituted colorant and the anhydride are present in relative amounts of at least about 1 mole of anhydride per every one mole of alcohol-substituted colorant.
24. A process according to claim 1 wherein bromination is carried out by adding elemental bromine.
25. A process according to claim 1 wherein bromination is carried out by generating it in situ by the addition of a combination of a bromide salt and a bromate salt.
26. A process according to claim 1 wherein the alcohol-substituent is converted to an ester-substituted colorant, and wherein the ester-substituted colorant and bromine are present during bromination in relative amounts of at least about 2 moles of Br 2 per every one mole of ester-substituted colorant.
27. A process according to claim 1 wherein the alcohol-substituent is converted to an ester-substituted colorant, and wherein the ester-substituted colorant and bromine are present during bromination in relative amounts of no more than about 4 moles of Br 2 per every one mole of ester-substituted colorant.
28. A process according to claim 1 wherein the reaction between the ester-substituted colorant and bromine during bromination is allowed to proceed for a period of time of at least about 5 hours.
29. A process according to claim 1 wherein the reaction between the ester-substituted colorant and bromine during bromination is allowed to proceed for a period of time of no more than about 24 hours.
30. A process according to claim 1 wherein Y is a hydrogen atom.
31. A process according to claim 1 wherein Y is a bromine atom.
32. A process according to claim 1 wherein n is 2.
33. A process according to claim 1 wherein the colorant thus formed is of the formula
34. A process according to claim 1 wherein the colorant thus formed is of the formula
35. A process according to claim 1 wherein the colorant thus formed is of the formula
36. A process according to claim 1 wherein the colorant thus formed is of the formula
37. A process according to claim 1 wherein R 1 is an unsubstituted alkylene group or an unsubstituted arylalkylene group.
38. A process according to claim 1 wherein R 1 is a substituted alkylene group or a substituted arylalkylene group.
39. A process according to claim 1 wherein hetero atoms selected from oxygen, nitrogen, sulfur, silicon, or phosphorus are present in the R 1 group.
40. A process according to claim 1 wherein no hetero atoms are present in the R 1 group.
41. A process according to claim 1 wherein R 1 is an alkylene group having at least about 2 carbon atoms.
42. A process according to claim 1 wherein R 1 is of the formula
43. A process according to claim 1 wherein R 2 is an unsubstituted alkyl group, an unsubstituted aryl group, an unsubstituted arylalkyl group, or an unsubstituted alkylaryl group.
44. A process according to claim 1 wherein R 2 is a substituted alkyl group, a substituted aryl group, a substituted arylalkyl group, or a substituted alkylaryl group.
45. A process according to claim 1 wherein hetero atoms selected from oxygen, nitrogen, sulfur, silicon, or phosphorus are present in the R 2 group.
46. A process according to claim 1 wherein no hetero atoms are present in the R 2 group.
47. A process according to claim 6 wherein R 1 is of the formula
48. A process according to claim 6 wherein R 2 is
49. A process according to claim 6 wherein R 2 is
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
50. A process according to claim 6 wherein the brominated ester-substituted colorant and the salt thereof are of the formulae
or mixtures thereof.
51. A process according to claim 6 wherein the brominated ester-substituted colorant and the salt thereof are of the formulae
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or mixtures thereof.
52. A process according to claim 7 wherein R 1 is of the formula
53. A process according to claim 7 wherein R 2 is
54. A process according to claim 7 wherein R 2 is
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
55. A process according to claim 7 wherein the brominated ester-substituted colorant and the salt thereof are of the formulae
or mixtures thereof.
56. A process according to claim 7 wherein the brominated ester-substituted colorant and the salt thereof are of the formulae
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or mixtures thereof.
57. A process according to claim 8 wherein R 1 is of the formula
58. A process according to claim 8 wherein R 2 is
59. A process according to claim 8 wherein R 2 is
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
60. A process according to claim 8 wherein the brominated urethane-substituted colorant and the salt thereof are of the formulae
or mixtures thereof.
61. A process according to claim 8 wherein the brominated urethane-substituted colorant and the salt thereof are of the formulae
or mixtures thereof, wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
62. A process according to claim 9 wherein R 1 is of the formula
63. A process according to claim 9 wherein R 2 is
64. A process according to claim 9 wherein R 2 is
wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
65. A process according to claim 9 wherein the brominated urethane-substituted colorant and the salt thereof are of the formulae
or mixtures thereof.
66. A process according to claim 9 wherein the brominated urethane-substituted colorant and the salt thereof are of the formulae
or mixtures thereof, wherein C 36 H 62+m is a branched alkylene group which may include unsaturations and cyclic groups, wherein m is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.Cited by (0)
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